• Journal of the Korean Chemical Society
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• v.13 no.4
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• pp.373-377
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• 1969

In order to determine the monomer reactivity ratio in copolymerization of acrolein, the copolymerization of acrolein with styrene, methyl methacrylate and vinyl acetate respectively was studied. The Q and e value of acrolein in each copolymerization were also calculated from those of monomer reactivity ratios, but the calculated values were slightly different from each other. The Q and e of acrolein for the system of acrolein-styrene copolymerization were Q = O.64 and e = O.62 respectively. Relations among the Q and e value, the composition and structure of copolymers and the mean sequence length in copolymerization were also discussed for acrolein copolymers.

• 제어로봇시스템학회:학술대회논문집
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• 1996.10b
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• pp.788-791
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• 1996

A mathematical model is developed for thermal solution copolymerization of styrene and acrylonitrile in a continuous stirred tank reactor(CSTR). Computational studies are carried out with the continuous copolymerization system model developed in this work to give the monomer conversion, copolymer composition and the average molecular weights of the copolymer. By performing the dynamic analysis of the reaction system, the polymer properties against the changes in the operating conditions are determined quantitatively. The cascade PID and fuzzy controller show satisfactory performances for both set point tracking and disturbance rejection. Especially, the fuzzy controller is superior to the PID controller.

• 제어로봇시스템학회:학술대회논문집
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• 1994.10a
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• pp.207-212
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• 1994

A mathematical model is developed for a batch reactor in which the free radical bulk copolymerization of styrene and acrylonitrile takes place. In this model, we introduce the free volume theory to quantify the diffusion controlled termination and propagation reactions, and develop a model for the chain length dependent termination reaction in the context of the pseudo kinetic rate constant method(PKRCM). The simulation results from this model are found to be in good agreement with experimental data under different copolymerization conditions. The present model can predict both the copolymer composition and the number and weight average molecular weights. These kinetic approaches provide greater insight into the performance of the batch reactor used for the free radical bulk copolymerization of styrene and acrylonitirle.

• Polymer(Korea)
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• v.24 no.1
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• pp.16-22
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• 2000

Poly(butylene terephthalate- co-oxybenzoate)(PBOT) containing mesogenic oxybenzoate units in the main chain was synthesized through ester exchange reaction by melt mixing of poly(butylene terephthalate)(PBT) and p-acetoxybenzoic acid (ABA). From the kinetics of the copolymerization reaction, the activation energies and the rate constants of homopolymerization and copolymerization, k$_{h}$ and k$_{c}$, could be determined. From the reaction conditions of different compositions, 4/6, 5/5, and 6/4 of PBT/ABA, at 250, 260, and 27$0^{\circ}C$, it was revealed that copolymerization between PBT and ABA proceeds on a pseudo-second order reaction if the ABA content and its conversion are low. In this case, the ratio of rate constants of homopolymerization to copolymerization was in the range from 1.08 to 3.17, indicating that the copolymer with more notable block character was obtained at the higher mole fraction of ABA and at higher temperature.e.e.

• Journal of the Korean Chemical Society
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• v.26 no.3
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• pp.179-187
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• 1982

The copolymerization of N-acryloylpyrrolidone and acrylonitrile was performed in N,N'-dimethylformamide at 50$^{\circ}$C and monomer reactivity ratio was obtained by using IR working curve and Fineman and Ross equation. ($r_1$ = 0.43, $r_2$ = 1.56) It is found that resulting copolymer is good polymeric initiator for anionic graft copolymerization of 2-pyrrolidone. Graft copolymers with polybutylamide (nylon-4) grafts onto poly(NAP-Co-AN) backbone were synthesized and the various effects on the graft copolymerization of 2-pyrrolidone were examined. The rate constants ($K_p$) of graft anionic polymerization at 40 and 50$^{\circ}$C were 2.82${\times}$10 and 2.93${\times}$10(l/mole, min), respectively.

• Applied Chemistry for Engineering
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• v.7 no.4
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• pp.623-632
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• 1996

The reactivity ratios, melting temperature and polymer morphology in propylene/butene-1 and propylene/hexene-1 copolymerization reactions were studied by examining comonomer compositions of resulting polymers. The catalysts used here are different in their supports which are silica(catalyst I) and magnesium(catalyst II). As the content of comonomer(butene-1 and hexene-1) increased in the copolymer, the melting temperature of the copolymer decreased. The morphology of polymer was amorphous in the range of comonomer(butene-1) composition over 40% in the propylene/butene-1 copolymerization and comonomer(hexene-1) composition over 80% in the propylene/hexene-1 copolymerization. The reactivity ratios were obtained by the Fineman-Ross and Kelen-$T{\ddot{u}}d{\tilde{o}}s$ methods.

• Journal of the Korean Chemical Society
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• v.20 no.4
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• pp.316-320
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• 1976

Based on the results of graft copolymerization to proteins, an attempt is made to derive the rate equations to explain the mechanism of Ce(IV) ion-initiated graft copolymerizations. In this system the oxidative termination by Ce(IV) $[R{\cdot}+ Ce(IV) ${\rightarrow}$ R(inert) + Ce(III) + H^+]$ is considered characteristic particularly in higher concentration of Ce(IV) ion. The change in the mode of termination reactions with change in Ce(IV) ion concentration makes possible the presence of an optimum Ce(IV) ion concentration for maximum graft copolymerization yield. This effect is reflected in presently derived equations.

• Journal of the Korean Chemical Society
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• v.62 no.3
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• pp.191-202
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• 2018

The aim of this work is to study Monte Carlo simulation of ethylene (co)polymerization over Ziegler-Natta catalyst as investigated by Chen et al. The results revealed that the Monte Carlo simulation was similar to sum square error (SSE) model to prediction of stage II and III of polymerization. In the case of activation stage (stage I) both model had slightly deviation from experimental results. The modeling results demonstrated that in homopolymerization, SSE was superior to predict polymerization rate in current stage while for copolymerization, Monte Carlo had preferable prediction. The Monte Carlo simulation approved the SSE results to determine role of each site in total polymerization rate and revealed that homopolymerization rate changed from site to site and order of center was different compared to copolymerization. The polymer yield was reduced by addition of hydrogen amount however there was no specific effect on uptake curve which was predicted by Monte Carlo simulation with good accuracy. In the case of copolymerization it was evolved that monomer chain length and monomer concentration influenced the rate of polymerization as rate of polymerization reduced from 1-hexene to 1-octene and increased when monomer concentration proliferate.

• 한국생물공학회:학술대회논문집
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• 2000.11a
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• pp.48-51
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• 2000

The poly(3-hydroxybutyrate) (PHB) synthase of Ralstonia. eutropha, which was produced by a recombinant strain E. coli and purified in one-step with a methyl-HIC column to a purity of more than 90%, was used to polymerize 3-hydroxypropionyl-CoA (3HPCoA) and to copolymerize 3HPCoA with 3-hydroxybutyryl-CoA (3HBCoA) in vitro. A $K_m$ of $189\;{\mu}M$ and a $k_{cat}$ of $10\;sec^{-1}$ were determined for the activity of the enzyme in the polymerization reaction of 3HPCoA based on the assumption that the dimer form of PHB synthase was the active form. Free coenzyme A was found to be a very effective competitive inhibitor for the polymerization of 3HPCoA with a $K_i$ of $85\;{\mu}M$. The maximum degree of conversion of 3HPCoA to polymer was less than 40 %. In the simultaneous copolymerization reactions of these two monomers, both the turnover number for the copolymerization reaction and the maximum degree of conversion of 3HPCoA and 3HBCoA to copolymers increased with an increase in the amount of 3HBCoA in the monomer mixture. However, the maximum conversion of 3HPCoA to a copolymer was less than 35 % regardless of the ratio of 3HPCoA to 3HBCoA. Block copolymers were obtained by the sequential copolymerization of the two monomers and these copolymers had a much narrower molecular weight distribution than those obtained by the simultaneous copolymerization of the same molar ratio of 3HPCoA and 3HBCoA.

• 제어로봇시스템학회:학술대회논문집
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• 1997.10a
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• pp.309-312
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• 1997

The dynamic characteristics of a continuous MMA/MA free-radical solution copolymerization reactor were studied. A mathematical model was developed and kinetic parameters which had been estimated in the previous work were used. With this model, bifurcation diagrams were constructed with various parameters as the bifurcation parameter to predict the region of stable operating conditions and to enhance the controller performance. It was shown that the steady-state multiplicity existed over wide ranges of residence time and jacket inlet temperature. Periodic solution branches were found to emanated from Hopf bifurcation points. Under certain conditions isola was also observed, which would result in poor performance of feedback controllers.